CN105612634B - Prepare method, anode materials for lithium secondary cells and the lithium secondary battery comprising the positive electrode of anode materials for lithium secondary cells - Google Patents

Prepare method, anode materials for lithium secondary cells and the lithium secondary battery comprising the positive electrode of anode materials for lithium secondary cells Download PDF

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CN105612634B
CN105612634B CN201580001598.9A CN201580001598A CN105612634B CN 105612634 B CN105612634 B CN 105612634B CN 201580001598 A CN201580001598 A CN 201580001598A CN 105612634 B CN105612634 B CN 105612634B
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positive electrode
metal oxide
lithium transition
transition metal
lithium
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CN105612634A (en
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郭益淳
曹昇范
尹汝俊
闵盛郁
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LG Corp
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Abstract

The present invention provides a kind of method preparing anode materials for lithium secondary cells, anode materials for lithium secondary cells and the lithium secondary battery for including the positive electrode.In particular it relates to a kind of method preparing anode materials for lithium secondary cells, the anode materials for lithium secondary cells prepared by method described above, and include the lithium secondary battery of the positive electrode, the method includes：The first step：Synthesize the lithium transition-metal oxide indicated by chemical formula 1；Second step：Lithium transition metal oxide powder is prepared by grinding the lithium transition-metal oxide；Third walks：The positive electrode comprising aluminum oxide coating layer is prepared by being mixed in aluminium oxide nano colloidal sol and disperseing the lithium transition metal oxide powder；And the 4th step：The dry positive electrode, [chemical formula 1] Li(1+a)(Ni(1‑a‑b‑c)MnbCoc)OnWherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.

Description

Prepare method, the anode materials for lithium secondary cells of anode materials for lithium secondary cells With the lithium secondary battery comprising the positive electrode
Technical field
Cross reference to related applications
This application claims in the Korean Patent Application No. 10-2014- submitted to Korean Intellectual Property Office on the 12nd of September in 2014 0121355 and the Korean Patent Application No. 10-2015-0128135's submitted to Korean Intellectual Property Office on the 10th of September in 2015 Equity, during the disclosure of the application is by reference to being hereby incorporated by reference in its entirety.
Technical field
The present invention relates to prepare the method for the anode materials for lithium secondary cells comprising gamma-alumina coating, aoxidized comprising γ The anode materials for lithium secondary cells of aluminized coating and lithium secondary battery comprising the positive electrode.
Background technology
As the technology development about mobile device has increased with demand, for the demand of the secondary cell as the energy Significantly increase.In these secondary cells, with high-energy density, high voltage, long circulation life and low self-discharge rate Lithium secondary battery has been commercialized and has been widely used.
In the preparation of lithium secondary battery, positive (positive electrode) and cathode (negative Electrode) using respectively can reversibly be embedded in and the material of deintercalate lithium ions.
Lithium transition-metal oxide such as LiCoO2、LiMn2O4、LiNiO2And LiMnO2It is widely used as secondary lithium batteries Positive electrode.However, having there is the novel-section for replacing these materials in terms of cost competitiveness, capacity and cycle characteristics The research of the exploitation of material.
Recently, it is proposed that by wherein in LiNiO2In a part of nickel taken by other transition metal (cobalt (Co) and manganese (Mn)) The various ternary lithium composite xoide (Li in generation1+x(NiaMnbCo1-a-b-x)O2(wherein -0.1≤x≤0.1,0≤a≤1,0≤x+a + b≤1) composition positive electrode.Although however, NiMnCo systems tertiary cathode material have excellent capacity and cycle characteristics, Stability under high temperature/high voltage may be low.
The characteristic for further increasing the positive electrode formed by these lithium transition-metal oxides can be modified by surface. It has been proposed, for example, that it is a kind of by prevent deterioration come extend positive electrode service life method, in the method by using The oxide of metal such as aluminium (Al), magnesium (Mg), zirconium (Zr), cobalt (Co), potassium (K), sodium (Na), calcium (Ca) and titanium (Ti), fluorine system material The surface of modified anode material is come on the surface of material or phosphate-based material coating positive electrode.
Korean Patent Publication No 10-2006-0051055 is disclosed a kind of to be prepared by using the processing based on water The method of the lithium transition-metal oxide of aluminum oxide coated, and Korean Patent Publication No 10-2013-0055654 is disclosed It is a kind of to use the dry-coated method method on aluminum oxide coated positive electrode surface.
However, conventional method has following limitation：Its process is complicated, and manufacturing cost increases, and because at dry-mixing The surface of positive electrode is damaged during reason and is difficult to obtain uniform Painting effect and low surface roughness.Therefore, because can Effective surface can be obtained to be modified, exploitation is needed to be capable of the method on the effectively surface of modified anode material.
Existing technical literature
Korean Patent Publication No 10-2006-0051055
Korean Patent Publication No 10-2013-0055654
Invention content
Technical problem
The method that one aspect of the present invention offer prepares anode materials for lithium secondary cells, the positive electrode include tool There is (γ) aluminum oxide coating layer of exceptional overcoat performance.
Another aspect of the present invention provides the anode materials for lithium secondary cells for including gamma-alumina coating.
Another aspect of the present invention provides the positive electrode for lithium secondary battery for including the positive electrode, and includes its lithium Secondary cell.
Technical solution
According to an aspect of the present invention, a kind of method preparing anode materials for lithium secondary cells, the method are provided Include the following steps：
The first step：Synthesize the lithium transition-metal oxide indicated by chemical formula 1；
Second step：Lithium transition metal oxide powder is prepared by grinding the lithium transition-metal oxide；
Third walks：By the way that the lithium transition metal oxide powder by system is mixed and disperseed in aluminium oxide nano colloidal sol The standby positive electrode comprising aluminum oxide coating layer；And
4th step：The dry positive electrode,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
According to another aspect of the present invention, a kind of positive electrode material for secondary battery is provided, the material includes：By chemistry The lithium transition metal oxide particle that formula 1 indicates；And aluminum oxide coating layer, on the surface of the lithium transition metal oxide particle The gamma-alumina phase of the upper amount for forming and include 95% or more,
Total surface area wherein based on the lithium transition metal oxide particle, the coverage rate of the aluminum oxide coating layer exist In the range of 30%~50%.
According to another aspect of the present invention, it provides comprising following lithium secondary battery：Anode；Cathode；It is arranged in anode Diaphragm between cathode；And electrolyte,
The wherein described anode includes the positive electrode indicated by chemical formula 2,
[chemical formula 2]
Li(1+a)(Ni(1-a-b-c)MnbCocM’x)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1,0<The integer that x≤1, n are 2 or 4, and M ' is with γ phases Al2O3。
In this case, after activation process and initial charge/discharge, based on the total weight of the electrolyte, the lithium is secondary Battery can have 900ppm HF contents below.
According to another aspect of the present invention, a kind of method preparing aluminium oxide nano colloidal sol is provided, the method includes： Aluminium oxide nano powder and solvent are mixed to prepare aluminium oxide nano powder suspension；Disperse the suspension with using ball mill Liquid is to prepare aluminium oxide nano colloidal sol, wherein the aluminium oxide nano colloidal sol includes the gamma-alumina phase of 99% or more amount.
Advantageous effect
As described above, according to the present invention, by using aluminium oxide nano colloidal sol on a part of surface of positive electrode shape At the gamma-alumina coating with low surface roughness and exceptional overcoat performance, it is secondary that the lithium comprising aluminum oxide coating layer can be prepared Positive electrode for battery material and lithium secondary battery comprising the positive electrode, high temperature and high voltage are improved in the positive electrode Stability, cycle characteristics and battery life.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) data of the gamma-alumina Nano sol of preparation example 1；
Fig. 2 is scanning electron microscope (SEM) figure on the surface of the positive electrode prepared according to the embodiment of the present invention 1；
Fig. 3 is that the SEM on the surface of the positive electrode prepared according to the embodiment of the present invention 2 schemes；
Fig. 4 is that the SEM on the surface of the positive electrode prepared according to comparative example 1 schemes；
Fig. 5 is that the SEM on the surface of the positive electrode prepared according to comparative example 2 schemes；
Fig. 6 be according to the experimental example 3 of the present invention to the cycle life characteristics of the secondary cell of embodiment 3 and comparative example 3 into The figure that row compares；And
Fig. 7 be according to the experimental example 3 of the present invention to the cycle life characteristics of the secondary cell of embodiment 4 and comparative example 4 into The figure that row compares.
Specific implementation mode
Hereinafter, it will be described in the present invention.It will be understood that the vocabulary used in the present specification and claims and Term is not necessarily to be construed as the meaning defined in usually used dictionary.It will be further understood that, it can be appropriate based on inventor Ground defines the meaning of vocabulary and term to best explain the principle of the present invention, vocabulary and term should be interpreted as having with its Meaning in the related field of the present invention and the background of technical concept.
Typically, it is proposed that the method for preparing the positive electrode comprising the aluminum oxide coating layer in film form, wherein using molten Agent such as alkoxide aoxidizes aluminium (Al), and the positive electrode powder of predetermined amount is placed in alumina solution and is mixed, then about High temperature sintering processing is carried out within the temperature range of 400 DEG C~about 600 DEG C.However, the case where stating wet mixed processing in use Under, because the aluminum oxide coating layer part in film form mutually exists as the boehmite with low-crystallinity, coating performance can It can be relatively low.Further, since aluminum oxide coating layer present on whole surface in positive electrode, causes the mobility of lithium ion to drop It is low, and the increase of the reduction and accident risk of this capacitance loss, battery life that may finally cause lithium secondary battery.
According to embodiment of the present invention, a kind of method preparing anode materials for lithium secondary cells is provided, it is described Method includes the following steps：
The first step：Synthesize the lithium transition-metal oxide indicated by chemical formula 1；
Second step：Lithium transition metal oxide powder is prepared by grinding the lithium transition-metal oxide；
Third walks：By the way that the lithium transition metal oxide powder by system is mixed and disperseed in aluminium oxide nano colloidal sol The standby positive electrode comprising aluminum oxide coating layer；And
4th step：The dry positive electrode,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
In this case, the total weight based on aluminum oxide coating layer, aluminum oxide coating layer can be with 95 weight % or more, preferably 99 weights Measure % or more, the amount of more preferable 100 weight % includes gamma-alumina phase.
In the method for the invention, as exemplary embodiments, lithium transition-metal oxide can be Li [Ni0.5Mn1.5- xCox]O4(0≤x≤0.1)、Li(Ni0.6Mn0.2Co0.2O2)、Li(Ni0.8Mn0.1Co0.1O2)、Li(Ni0.5Mn0.3Co0.2O2)、Li (Ni1/3Mn1/3Co1/3O2) or LiCoO2。
In addition, in addition to the lithium transition-metal oxide indicated by chemical formula 1, lithium transition-metal oxide can also include logical Common positive electrode lithium transition-metal oxide in the art, specifically, ternary lithium transition-metal oxide is such as LiNi1-x-y-zCoxM1yM2zO2(wherein M1 and M2 are each independently selected from aluminium (Al), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), any one of vanadium (V), chromium (Cr), titanium (Ti), tungsten (W), tantalum (Ta), magnesium (Mg) and molybdenum (Mo), and x, y and z are respectively It independently is the atomic fraction of oxide forming elements, wherein 0≤x<0.5,0≤y<0.5,0≤z<0.5, and x+y+z≤1), With selected from LiNiO2(LNO)、LiMnO2(LMO) and LiMn2O4In single material or its mixture of two or more. The mixture can be then sintered to carry out synthesis lithium mistake by mixing lithium precursor and other transition metal precursors in a mixer Cross the first step of metal oxide.In such a case it is possible to carried out in 1000 DEG C~1100 DEG C of temperature range about 6 hours~ Mixing in about 12 hours, specifically 10 hours and sintering.
In addition, according to the method for the present invention, in second step, by grinding the lithium transition-metal oxygen obtained in the first step Compound can prepare the lithium transition metal oxide powder with about 10 μm~about 30 μm, particularly 18 μm of grain size.Second In the case that the grain size of the lithium transition metal oxide powder obtained in step is more than 30 μm, sheet resistance may increase.Wherein In the case that grain size is less than 10 μm, specific surface area may increase, it may finally cause initial capacity in subsequent processing as a result, With the reduction of cycle.
In addition, in the method for the invention, can carry out walking in third under the speed of 300rpm using mixer In lithium transition metal oxide powder dispersion process.
It in the third step, can be with 1:80~1:100 weight ratio mixing lithium transition metal oxide powder and aluminium oxide is received Rice colloidal sol.In the case where the mixing ratio of aluminium oxide nano colloidal sol is by weight being less than 80, because it is dry-mixed to be likely difficult to progress half It closes, so the roughness of aluminum oxide coating layer may increase and coating performance may deteriorate.On the contrary, aluminium oxide nano is molten wherein The mixing ratio of glue by weight be more than 100 in the case of, drying time may increase and coating process may take it is longer.
In addition, in the third step, lithium transition metal oxide powder can be directly dispersing in aluminium oxide nano colloidal sol, Or lithium transition-metal oxide powder can prepared by spraying the lithium transition metal oxide powder in organic solvent Disperseed after last solution.
In this case, it is desirable to use the organic solvent with low boiling point (bp) so that can easily steam at low temperature Send out organic solvent.The representative instance of organic solvent can be 1- methoxy-2-propanols, ethyl alcohol, methanol or isopropanol.Based on anode The total weight of material can use organic solvent with the amount of 70 weight of weight %~99 %.It is more than 99 weights in the amount of organic solvent It measures % or less than in the case of 70 weight %, coating homogeneity may be decreased.
In the method for the invention, the temperature range in 130 DEG C~350 DEG C, particularly 150 DEG C~300 DEG C can be passed through Interior progress low-temperature sintering carries out the drying of the 4th step.
In addition, the method for the present invention can further include the 5th step for being sintered dry positive electrode after the 4th step.
In such a case it is possible to carry out the 5th step by carrying out high temperature sintering within the temperature range of 400 DEG C~800 DEG C Sintering.
That is, method according to the invention it is possible to only in the table of positive electrode by carrying out the drying of the 4th step The gamma-alumina coating with low surface roughness and exceptional overcoat performance is formed on face.Furthermore, it is possible to by after the drying into One step carries out high temperature sintering and obtains the better Painting effect of gamma-alumina coating.
It is molten that the aluminium oxide nano used in the method for preparing the positive electrode of the present invention can be prepared by the following method Glue, the method includes：
Mixed oxidization aluminum nano-powder and solvent are to prepare aluminium oxide nano powder suspension；And disperseed using ball mill The suspension to prepare aluminium oxide nano colloidal sol,
The wherein described aluminium oxide nano colloidal sol includes the gamma-alumina phase of 99% or more amount.
Can by using the ball mill dispersion solvent and aluminium oxide nano powder for using high-speed rotating atomizing nozzle, To be disperseed.
In such a case it is possible to utilize ball mill to carry out under center rotating speed more than 3000rpm (linear velocity 10m/ seconds) The dispersion of suspension.In addition, slurry input rate during dispersion can be 600cc/ minutes, and can use comprising The composition of 10L dispersion liquids is disperseed.In the case where rotating speed is less than values above, dispersibility may be decreased, and in slurry In the case that input rate is more than values above, pearl may be discharged.The diameter of pearl in ball mill can 0.05mm~ In the range of 0.1mm.
In the method for preparing aluminium oxide nano colloidal sol, it is expected that being aoxidized in preparation using the solvent with low bp to meet Rapid draing condition during aluminium Nano sol.The representative instance of solvent can be organic solvent such as 1- methoxy-2-propanols, second Alcohol, methanol or isopropanol.
Based on the total amount of aluminium oxide nano colloidal sol, the amount of contained solvent can be 70 weight of weight %~99 %.Molten In the case that the amount of agent is more than 99 weight %, processing time may increase, and in the case where the amount of solvent is less than 70 weight %, Due to the excessive concentration of Al, it is possible to create unstable coating.
Aluminium oxide nano powder is the gamma-alumina nanometer powder with 1nm~50nm grain sizes, and wherein surface charge can be with There can be low-crystallinity for positive (+) and aluminium oxide nano powder.
In addition, the aluminium oxide nano colloidal sol prepared can include the aluminium oxide nano powder with 1nm~20nm grain sizes.
It therefore, in the present invention, can be in anode by using gamma-alumina Nano sol, using half-dried coating method The γ with low surface roughness, exceptional overcoat performance and excellent lithium ionic mobility is formed on a part of surface of material to aoxidize Aluminized coating.
That is, the method for using typical dry pigmentation to prepare the positive electrode comprising aluminum oxide coating layer, not only It may be there is a phenomenon where generating dust during mixed process, and may be because that the surface of positive electrode is damaged by dry mixing process Without forming uniform coating.In addition, typically wherein alumina is aoxidized to prepare by using solvent such as alkoxide for using The method that the wet mixing method of aluminized coating forms aluminum oxide coating layer, because aluminum oxide coating layer part is with the boehmite phase with low-crystallinity In the presence of it is possible that forming the aluminum oxide coating layer with low coating performance in the whole surface of positive electrode.In addition, because Even coating may be difficult, it is possible that influencing the absorption and release of lithium ion.
On the contrary, half dry-coating process of the gamma-alumina Nano sol for using the present invention, because gamma-alumina particle has There are very fine hole, high porosity and bigger serface, so half dry-coating process can pass through the absorption property of raising coating And improve Painting effect.Therefore, different from regular situation, even if without high temperature sintering, coating can also have tight adhesion To the physical property on a part of surface of positive electrode particle.In addition, the shape on a part of surface of the positive electrode of the present invention At gamma-alumina coating do not cover the whole surface of positive electrode, but formed on a part of surface.Therefore, because oxidation Aluminized coating does not influence the redox reaction of lithium ion, so the mobility of lithium ion can be excellent.It is thus possible to increase The capacity of lithium secondary battery and it may insure the life characteristic under high temperature and high voltage.
Particularly, since the gamma-alumina coating formed on a part of surface of the positive electrode of the present invention does not include suddenly Nurse stone phase, so as shown in following formulas, gamma-alumina coating can selectively with due to being included in non-water power The HF for solving the moisture in liquid and generating reacts and serves as scavenger.Therefore, with the typical oxidation aluminized coating phase comprising boehmite phase Than, by prevent positive electrode surface damage and be significantly improved due to being led comprising residual moisture in the electrolytic solution The deterioration of the battery behavior of cause, gamma-alumina coating can the exhibitions in terms of service life, cycle and output characteristics at a room temperature and a high temperature Existing excellent battery performance (referring to following formulas).
[reaction equation]
Al2O3+HF→AlF3+H2O
In addition, according to the embodiment of the present invention, positive electrode material for secondary battery is provided, it includes：
The lithium transition metal oxide particle indicated by chemical formula 1；With
Aluminum oxide coating layer forms on the surface of the lithium transition metal oxide particle and includes 95% or more The gamma-alumina phase of amount,
Total surface area wherein based on the lithium transition metal oxide particle, the coverage rate of the aluminum oxide coating layer exist In the range of 30%~50%,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
About the positive electrode of the present invention, aluminum oxide coating layer does not cover the whole surface of positive electrode, but partly applies Cloth is on the 30%~50% of the whole table area of lithium transition metal oxide particle.Therefore, because aluminum oxide coating layer does not influence The absorption and release of lithium ion, it is hereby achieved that excellent lithium ionic mobility.In the case where coverage rate is higher than 50%, lithium The absorption and release of ion may be affected, and in the case where coverage rate is less than 30%, because spreading area may be small, So recurring number may be reduced due to the side reaction with electrolyte.
In this case, aluminum oxide coating layer is not concentrated on the side on positive electrode surface, but in the oxygen of particle shape (coating) can be uniformly dispersed on a part of surface of positive electrode by changing aluminized coating.
In addition, the aluminum oxide coating layer formed on a part of surface of positive electrode can be with single or multiple lift structure. In this case, in order to improve the life characteristic and high-temperature storage characteristics of battery, oxygen can be suitably adjusted in a certain range Change the thickness of aluminized coating, and is not particularly limited.However, in the case where aluminum oxide coating layer is blocked up, due to aluminum oxide coating layer May influence capacity and output characteristics, thus the thickness of aluminum oxide coating layer can be 30nm hereinafter, such as 20nm or less.
In addition, the aluminum oxide coating layer formed on a part of surface of positive electrode can have 10nm on the whole surface Surface roughness (Ra) below.
In the present invention, the total weight based on positive electrode, the content of the aluminium in aluminum oxide coating layer can be 5ppm~ 100ppm.In the case where the amount of aluminium is less than 5ppm, since the amount of the aluminium in being coated with used in surface is small, so in positive material Coating is sufficiently formed on the surface of material to have any problem.On the contrary, in the case where the amount of aluminium is more than 100ppm, due to foring thickness Coating is to reduce the mobility of lithium ion, so resistance may increase and output characteristics may be impacted.
In addition, according to the embodiment of the present invention,
There is provided anode of secondary cell, it includes in positive electrode and selectively conductive dose, adhesive and filler extremely A kind of few additive,
Wherein positive electrode includes the lithium transition metal oxide particle indicated by chemical formula 1；With
Aluminum oxide coating layer forms on the surface of the lithium transition metal oxide particle and includes 95% or more The gamma-alumina phase of amount, wherein the total surface area based on the lithium transition metal oxide particle, the aluminum oxide coating layer covers Lid rate is in the range of 30%~50%.
In this case, the total weight based on the mixture comprising positive electrode, usually with 1 weight of weight %~30 %'s Amount addition conductive agent.
Can use arbitrary conductive agent without especially limiting, as long as its with suitable electric conductivity without drawing in the battery Play unfavorable chemical change.For example, conductive agent may include conductive material such as：Graphite, carbon black, acetylene black, Ketjen black, slot Black, furnace black, lampblack, thermal crack black or conductive fiber such as carbon fiber and metallic fiber；Metal powder such as fluorocarbon powder End, aluminium powder and nickel by powder；Conductive whiskers such as ZnOw and potassium titanate crystal whisker；Conductive metal oxide such as titanium oxide；Or Polyphenylene derivatives.The specific example of business conductive agent may include product (Chevron chemical company of acetylene black system (Chevron Chemical Company), Denka black (private limited partnership of Denka Singapore (Denka Singapore Private Limited)) or Gulf Oil Corporation (Gulf Oil Company), Ketjen black, carbonic acid Asia second Ester (EC) is product (Armak companies (Armak Company)), Vulcan XC-72 (Cabot companies (Cabot )) and Super P (Timcal Graphite＆Carbon) Company.
Adhesive is to assist the bonding between active material and conductive agent and the ingredient with the bonding of current-collector.Based on packet The total weight of mixture containing positive electrode usually adds adhesive with the amount of 1 weight of weight %~30 %.The example of adhesive May include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, Polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonation EPDM, butadiene-styrene rubber, fluorubber, various copolymers etc..
Filler is the ingredient for being alternatively used for inhibiting electrode expansion.Filler is not particularly limited, as long as it is in electricity Do not cause unfavorable chemical change in pond and is fibrous material.The example of filler may include that olefin polymer is such as poly- Ethylene and polypropylene；With fibrous material such as glass fibre and carbon fiber.
The present invention by providing anode of secondary cell as follows：It is coated with anode current collector using slurry, then by coating Anode current collector is dried and rolls, wherein by mixing positive electrode with solvent such as n-methyl-2-pyrrolidone (NMP) To prepare the slurry.
Usually anode current collector is manufactured into about 3 μm~about 500 μm of thickness.Anode current collector does not limit especially System, if its with high conductivity without causing unfavorable chemical change in the battery.Anode current collector can be by for example Stainless steel, aluminium, nickel, titanium are fired carbon, or are formed using a kind of surface-treated aluminium or stainless steel in carbon, nickel, titanium, silver etc.. Current-collector can with uneven surface with improve positive electrode active materials adhesion strength and can with it is variously-shaped as film, Any one of piece, foil, net, porous body, foams, non-woven body etc..
In addition, according to the embodiment of the present invention,
Lithium secondary battery is provided, it includes：Anode, cathode, the diaphragm and electrolyte of setting between a positive electrode and a negative electrode,
Wherein anode includes the positive electrode indicated by chemical formula 2,
[chemical formula 2]
Li(1+a)(Ni(1-a-b-c)MnbCocM’x)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1,0<The integer that x≤1, n are 2 or 4, and M ' is with γ phases Al2O3。
In this case, after activation process and initial charge/discharge, the total weight based on electrolyte, lithium secondary battery can be with With 900ppm HF contents below.
In addition, after 10 charge and discharge cycles, the total weight based on electrolyte, lithium secondary battery can have 100ppm with Under HF contents.
In the lithium secondary battery of the present invention, the gamma-alumina coating being coated on the surface of positive electrode can be selective It reacts to serve as scavenger with the HF generated due to the moisture included in nonaqueous electrolytic solution in ground.For example, by predetermined amount The moisture of (5000ppm) is added to the electrolyte of lithium secondary battery and adds Al2O3Positive pole powder before and after coating Afterwards, if measuring HF contents after a week, for using the secondary cell for the positive pole powder for not forming coating thereon, HF contents For 5000ppm, but it is understood that being coated with Al for using2O3Positive pole powder secondary cell, HF contents are decreased to less than 1000ppm, particularly 900ppm or less.
In the lithium secondary battery, cathode is prepared by such as getting off：It is coated with using negative material containing a negative electrode active material Then negative electrode current collector dries negative electrode current collector.If desired, can include ingredient such as conductive agent, bonding in negative material Agent and filler.
The example of negative electrode active material may include carbon and graphite material such as natural graphite, electrographite, expanded graphite, carbon Fiber, hard carbon, carbon black, carbon nanotube, fullerene and activated carbon；It can be with alloyed metal (AM), such as Al, silicon (Si), tin with lithium (Sn), silver-colored (Ag), bismuth (Bi), Mg, zinc (Zn), indium (In), germanium (Ge), lead (Pb), palladium (Pd), platinum (Pt) and Ti, and contain this The compound of a little elements；Carbon and graphite material and metal and its compound of compound；Nitride containing lithium.Wherein it is possible to use Carbon system active material, silicon systems active material, tin system active material or silicon-carbon system active material, and can be individually or with its two kinds Or more these materials are applied in combination.
Negative electrode current collector is typically made into about 3 μm~about 500 μm of thickness.Negative electrode current collector is not particularly limited, As long as its is conductive without causing unfavorable chemical change in the battery.Negative electrode current collector can be by for example following shape At：Copper, stainless steel, aluminium, nickel, titanium fire carbon, using a kind of surface-treated copper or stainless steel in carbon, nickel, titanium, silver etc., Aluminium cadmium alloy etc..In addition, as anode current collector, negative electrode current collector can have fine rough surface to live with cathode to improve The adhesion strength of property material.Negative electrode current collector can have variously-shaped such as film, piece, foil, net, porous body, foams, non-woven fabrics Body etc..
Diaphragm is arranged between a positive electrode and a negative electrode, and uses the thin insulating with high ion permeability and mechanical strength Film.Diaphragm usually has 0.01 μm~10 μm of aperture and 5 μm~300 μm of thickness.For example, by olefin polymer for example poly- third The piece or non-woven fabrics that alkene is formed；Diaphragm is may be used as with chemical resistance and hydrophobic glass fibre or polyethylene.When will consolidate When body electrolyte such as polymer is used as electrolyte, which is also used as diaphragm.
Nonaqueous electrolytic solution containing lithium salt is formed by electrolyte and lithium salts, and in addition to non-aqueous organic solvent, organic solid electricity Solution matter and inorganic solid electrolyte are also used as electrolyte.
The example of non-aqueous organic solvent may include aprotic organic solvent, such as n-methyl-2-pyrrolidone, polypropylene carbonate Ester, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1,2- dimethoxy-ethane, four Hydroxyl French Franc (tetrahydroxy franc), 2- methyltetrahydrofurans, dimethyl sulfoxide (DMSO), 1,3-dioxolane, formamide, two Methylformamide, dioxolanes, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, two Butyl oxide link derivative, sulfolane, methyl sulfolane, 1,3- dimethyl -2- imidazolidinones, polypropylene carbonate ester derivant, tetrahydrochysene furan It mutters derivative, ether, methyl propionate and ethyl propionate.
The example of organic solid electrolyte may include polythene derivative, polyethylene oxide derivant, polypropylene oxide Derivative, phosphate ester polymer, poly-stabilized lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and contain ion Dissociate the polymer of group.
The example of inorganic solid electrolyte may include the nitride, halide and sulfate of lithium (Li), such as Li3N、 LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH、 And Li3PO4-Li2S-SiS2。
Lithium salts is to hold diffluent material in nonaqueous electrolyte, and for example may include LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi, chloroborane lithium, lower aliphatic carboxylic acid's lithium, tetraphenylboronic acid lithium and imino group lithium.
In addition, in order to improve charge-discharge characteristic and anti-flammability, can will for example pyridine, triethyl phosphite, triethanolamine, Cyclic ethers, ethylenediamine, glycol dimethyl ether, hexaphosphoric acid triamide, nitrobenzene derivative, sulphur, quinoneimine dye, N- replaceAzoles Alkanone, N, imidazolidine, glycol dialkyl ether, ammonium salt, pyrroles, 2-methyl cellosolve, the alchlor etc. of N- substitutions are added to Electrolyte.In some cases, can further include halogen-containing solvent such as carbon tetrachloride and trifluoro-ethylene to assign noninflammability, it can To further include carbon dioxide gas to improve high-temperature storage characteristics, and can further include fluoroethylene carbonate (FEC), propylene Sultone (PRS) etc..
Secondary cell is not only used in the battery unit of the power supply as midget plant, and can also be comprising more Be used as element cell in the medium-sized and large-sized battery module of a battery unit, the battery module be used as needing high-temperature stability, The power supply of the medium-sized and large-scale plant of cycle life characteristics and high rate capability.
It is medium-sized to be with large-scale plant preferred embodiment：Electric tool；Electric vehicle (EV) comprising electric vehicle mixes Close power electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV)；Electric bicycle comprising electrical salf-walking Vehicle and Electric Scooter；Electric golf cart；With the electrical storage device of the electric drive by motor, but it is described it is medium-sized and Large-scale plant is without being limited thereto.
Although the present invention has shown and described with reference to its illustrative embodiments, it should be understood that in the master without departing substantially from the present invention In the case of purport and range, wherein various modifications may be made.Therefore, the scope of the present invention should not necessarily be limited by the above embodiment, And it should be determined by appended claims and its equivalents.
Embodiment
Preparation example 1：The preparation of aluminium oxide nano colloidal sol
By gamma-alumina powder (Alu-C, the dimension D of 1000g50) and 9000g 1- methoxy-2-propanols mixing, then Disperse to aoxidize to prepare the γ comprising the gamma-alumina nanometer powder with 10nm grain sizes using vertical ball mill (Apex mill) Aluminium Nano sol.Aluminium oxide nano colloidal sol is dried and carries out X-ray diffraction (XRD) and measures (referring to Fig. 1).
Embodiment 1：The preparation (low temperature drying) of positive electrode containing gamma-alumina coating
By the Li of 48.25g2CO3With the Co of 101.75g3O4It is placed in mixed powder machine and mixes 5 minutes.Then, it is being sintered At a temperature of 1000 DEG C be sintered within 10 hours in stove.The block obtained after sintering is placed in grinder and is ground to 18 μm diameter to prepare lithium transition-metal oxide (LiCoO2)。
Next, the aluminium oxide nano colloidal sol and lithium transition-metal oxide of preparation example 1 are placed on Versatile apparatus (MP5) In and mix to prepare the positive electrode for including gamma-alumina coating.Then, positive electrode is dried at a temperature of 200 DEG C 10 hours.Fig. 2 is electron microscope (SEM) figure on the surface of the positive electrode prepared.
Embodiment 2：The preparation (high temperature sintering) of positive electrode containing gamma-alumina coating
It is prepared for positive electrode by with identical mode in embodiment 1, the difference is that will prepare in embodiment 1 Positive electrode be further sintered 10 hours at a temperature of about 500 DEG C.Fig. 3 is the electronic display on the surface of the positive electrode prepared Micro mirror (SEM) figure.
Embodiment 3：The preparation of secondary cell
By the positive electrode with the aluminum oxide coating layer being formed on prepared in embodiment 1, conductive agent and bonding Agent is with 96:2:2 weight ratio is mixed to prepare anode sizing agent.Using the slurry be coated with Al foils, then rolled and dried with Prepare anode of secondary cell.Anode is stamped into coin-shaped and is then prepared for Coin shape secondary cell.
Li metals are used as to the negative electrode active material of secondary cell, and use wherein 1M LiPF6It is dissolved in carbonic ester Electrolyte in electrolyte.
Embodiment 4：The preparation of secondary cell
By the positive electrode with the aluminum oxide coating layer being formed on prepared in example 2, conductive agent and bonding Agent is with 96:2:2 weight ratio is mixed to prepare anode sizing agent.Using the slurry be coated with Al foils, then rolled and dried with Prepare anode of secondary cell.Anode is stamped into coin-shaped and is then prepared for Coin shape secondary cell.
Li metals are used as to the negative electrode active material of secondary cell, and use wherein 1M LiPF6It is dissolved in carbonic ester Electrolyte in electrolyte.
Comparative example 1：Positive electrode (low-temperature sintering) with the aluminum oxide coating layer comprising the boehmite phase being formed on
Aluminium (Al) oxidation is prepared for alumina solution using solvent such as alkoxide, then by being mixed in alumina solution And the positive electrode powder (LiCoO of dispersion predetermined amount2) to prepare to have it is formed on the positive material of aluminum oxide coating layer Material.
Next, the positive pole powder of preparation is dried 10 hours at a temperature of 200 DEG C.Fig. 4 is the positive electrode prepared Surface electron microscope (SEM) figure.
Comparative example 2：Preparation (the high temperature of positive electrode with the aluminum oxide coating layer comprising the boehmite phase being formed on Sintering)
It is prepared for positive electrode by the identical mode in comparative example 1, the difference is that will be prepared in comparative example 1 Positive electrode be further sintered 10 hours at a temperature of about 500 DEG C.Fig. 5 is the electronic display on the surface of the positive electrode prepared Micro mirror (SEM) figure.
Comparative example 3：The preparation of secondary cell
By the positive electrode with the aluminum oxide coating layer being formed on prepared in comparative example 1, conductive agent and bonding Agent is with 96:2:2 weight ratio is mixed to prepare anode sizing agent.Using the slurry be coated with Al foils, then rolled and dried with Prepare anode of secondary cell.Anode is stamped into coin-shaped and is then prepared for Coin shape secondary cell.Li metals are used as Negative electrode active material, and use wherein 1M LiPF6The electrolyte being dissolved in carbonic ester electrolyte.
Comparative example 4：The preparation of secondary cell
By the positive electrode with the aluminum oxide coating layer being formed on prepared in comparative example 2, conductive agent and bonding Agent is with 96:2:2 weight ratio is mixed to prepare anode sizing agent.Using the slurry be coated with Al foils, then rolled and dried with Prepare anode of secondary cell.Anode is stamped into coin-shaped and is then prepared for Coin shape secondary cell.Li metals are used as Negative electrode active material, and use wherein 1M LiPF6The electrolyte being dissolved in carbonic ester electrolyte.
1. surface morphologic observation of experimental example
Utilize the table for each positive electrode that electron microscope observation is prepared in Examples 1 and 2 and comparative example 1 and 2 Face is to measure the coverage rate of each aluminum oxide coating layer.
According to measurement result, it can be confirmed and formed respectively on the surface of the positive electrode of Examples 1 and 2 with about The aluminum oxide coating layer of 30%~about 50% coverage rate, but shape is distinguished in the whole surface of the positive electrode in comparative example 1 and 2 At the aluminum oxide coating layer for being in film shape.
In this case, the surface roughness (Ra) on the surface of the positive electrode of Examples 1 and 2 be 10nm (referring to Fig. 2 and 3), but there is the dispersibility of difference due to undergoing the positive electrode of low sintering comparative example 1 and 2 to there are big particle, So can be confirmed that coating performance is low, for example, the surface roughness (Ra) on the surface of the positive electrode of comparative example 1 and 2 is 100nm (referring to Figure 4 and 5).
The comparison of 2. scavenger effect of experimental example
Make embodiment 3 and 4 and the electrolyte of secondary cell of comparative example 3 and 4 be exposed to outdoor air to generate HF, to It is prepared for the lithium secondary battery that wherein total weight of the HF contents based on electrolyte is 10500ppm (amount of moisture of 10000ppm).With Afterwards, the amount that the positive electrode prepared in Examples 1 and 2 is added to the wherein moisture of 100g is maintained at 10000ppm levels Each electrolyte, and measure stay HF contents (concentration) in the electrolyte after a predetermined time has passed.It is illustrated in table 1 Its result.
In this case, it using 848/801 Instrument measuring HF contents of Metrohm, is being electrolysed by using aqueous slkali titration Acid (HF) in liquid identifies pH levels, so as to evaluate the concentration of HF.
[table 1]
As shown in Table 1, for the secondary cell of comparative example 3 and 4, it is possible to understand that compared with embodiment 3 and 4, in electricity The rate of descent of HF contents at any time solved in liquid significantly reduces.As a result, the part in the positive electrode of the present invention can be confirmed The gamma-alumina coating of upper formation serves as HF scavengers.
Experimental example 3.
Cycling life test is carried out to the secondary cell prepared in embodiment 4 and comparative example 4, and is opened up in figs. 6 and 7 Its result is shown.Specifically, the volume change for carrying out 50 cycles with the voltage of 0.5C/1C and 4.45V at 45 DEG C is tested.
Two with comparative example 4 can be confirmed for the secondary cell of the embodiment 4 recycled based on 50 times with reference to Fig. 6 and 7 Primary cell is compared, and reduction and the cycle characteristics of capacity are improved.That is, can be confirmed the secondary cell of the present invention in basis Do not have big difference in the volume change of cycle, still, for the secondary cell of comparative example, because of the positive electrode for being included Scavenger not enough is served as, so cycle life characteristics significantly reduce.

Claims (24)

1. a kind of method preparing anode materials for lithium secondary cells, the described method comprises the following steps：
The first step：Synthesize the lithium transition-metal oxide indicated by chemical formula 1；
Second step：Lithium transition metal oxide powder is prepared by grinding the lithium transition-metal oxide；
Third walks：Packet is prepared by being mixed in aluminium oxide nano colloidal sol and disperseing the lithium transition metal oxide powder The positive electrode of salic coating, wherein the lithium transition metal oxide powder and the aluminium oxide nano colloidal sol are with 1:80 To 1:100 weight ratio mixing, and the wherein described aluminium oxide nano colloidal sol is prepared by a method comprising the following steps：
Mixed oxidization aluminum nano-powder and solvent are to prepare aluminium oxide nano powder suspension, wherein being based on aluminium oxide nano colloidal sol Total amount, the amount of contained solvent is 70~99 weight %, and
Disperse the suspension using ball mill to prepare aluminium oxide nano colloidal sol, wherein the aluminium oxide nano colloidal sol includes 99% The gamma-alumina phase of above amount；And
4th step：By carrying out low-temperature sintering in 130~350 DEG C of temperature ranges, thus the dry positive electrode,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
2. method described in claim 1, wherein the total weight based on the aluminum oxide coating layer, the aluminum oxide coating layer includes 95 The gamma-alumina phase of the amount of weight % or more.
3. method described in claim 1, wherein the lithium transition-metal oxide is Li (Ni0.6Mn0.2Co0.2O2)、Li (Ni0.8Mn0.1Co0.1O2)、Li(Ni0.5Mn0.3Co0.2O2)、Li(Ni1/3Mn1/3Co1/3O2) or LiCoO2。
4. method described in claim 1, wherein the lithium transition metal oxide powder ground in the second step Grain size is in the range of 10 μm~30 μm.
5. method described in claim 1, wherein in third step, the lithium transition metal oxide powder is direct It is dispersed in the aluminium oxide nano colloidal sol, or
Lithium transition metal oxide powder is being prepared by spraying the lithium transition metal oxide powder in organic solvent Disperseed after solution.
6. the method described in claim 5, wherein the organic solvent is 1- methoxy-2-propanols, ethyl alcohol, methanol or isopropyl Alcohol.
7. the method described in claim 5, wherein the total weight based on the positive electrode, the dosage of the organic solvent is 70 The weight of weight %~99 %.
8. method described in claim 1 further includes the 5th step for being sintered dry positive electrode after the 4th step.
9. method according to any one of claims 8, wherein the sintering of the 5th step is within the temperature range of 400 DEG C~1200 DEG C It carries out.
10. method described in claim 1, wherein the suspension carried out using the ball mill is dispersed in 3000rpm Center rotating speed under carry out.
11. method described in claim 1, wherein range of the diameter of the pearl in the ball mill in 0.05mm~0.1mm It is interior.
12. method described in claim 1, wherein the solvent is 1- methoxy-2-propanols, ethyl alcohol, methanol or isopropanol.
13. method described in claim 1, wherein the grain size at alumina nano powder end is in the range of 1nm~50nm.
14. method described in claim 1, wherein the alumina nano powder end is gamma-alumina nanometer powder.
15. method described in claim 1, wherein the aluminium oxide nano colloidal sol includes the oxidation with 1nm~20nm grain sizes Aluminum nano-powder.
16. a kind of positive electrode material for secondary battery, is obtained by method of claim 1, the positive electrode includes：
The lithium transition metal oxide particle indicated by chemical formula 1；With
Aluminum oxide coating layer forms on the surface of the lithium transition metal oxide particle and includes 95% or more amount Gamma-alumina phase,
Total surface area wherein based on the lithium transition metal oxide particle, the coverage rate of the aluminum oxide coating layer 30%~ In the range of 50%,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
17. the positive electrode material for secondary battery described in claim 16, wherein the thickness of the aluminum oxide coating layer is 30nm or less.
18. the positive electrode material for secondary battery described in claim 16, wherein the aluminum oxide coating layer has on the whole surface The surface roughness (Ra) of 10nm.
19. the positive electrode material for secondary battery described in claim 16, wherein the total weight based on the positive electrode, described The amount of aluminium is in the range of 5ppm~100ppm in aluminum oxide coating layer.
20. a kind of anode of secondary cell, the anode include：
The positive electrode obtained by method of claim 1；With
Selectively conductive dose, adhesive and filler in addition to the positive electrode,
The wherein described positive electrode includes the lithium transition metal oxide particle indicated by chemical formula 1；With
Aluminum oxide coating layer forms on the surface of the lithium transition metal oxide particle and includes 95% or more amount Gamma-alumina phase,
Total surface area wherein based on the lithium transition metal oxide particle, the coverage rate of the aluminum oxide coating layer 30%~ In the range of 50%,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
21. lithium secondary battery, it includes：
The anode of secondary cell of claim 20；
Cathode；
Diaphragm between the anode and the cathode is set；With
Electrolyte,
The wherein described anode includes the positive electrode indicated by chemical formula 2,
[chemical formula 2]
Li(1+a)(Ni(1-a-b-c)MnbCocM’x)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1,0<The integer that x≤1, n are 2 or 4, and M ' is the Al with γ phases2O3。
22. the lithium secondary battery described in claim 21 is based on the electrolyte wherein after activation process and initial charge/discharge Total weight, the lithium secondary battery have 900ppm HF contents below.
23. the lithium secondary battery described in claim 21, wherein after 50 charging cycles, the gross weight based on the electrolyte Amount, the lithium secondary battery have 100ppm HF contents below.
24. the lithium secondary battery described in claim 21, wherein the anode includes：
The lithium transition metal oxide particle indicated by chemical formula 1；With
Aluminum oxide coating layer forms on the surface of the lithium transition metal oxide particle and includes 95% or more amount Gamma-alumina phase,
Total surface area wherein based on the lithium transition metal oxide particle, the coverage rate of the aluminum oxide coating layer 30%~ In the range of 50%,
[chemical formula 1]
Li(1+a)(Ni(1-a-b-c)MnbCoc)On
Wherein 0≤a≤0.1,0≤b≤1,0<C≤1, and the integer that n is 2 or 4.
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